CN103819316B - Curable polyfluorene and the application as heat-stable material thereof - Google Patents

Abstract

The present invention relates to curable polyfluorenes and their use as heat-resistant materials. Specifically, the present invention provides a compound represented by the following formula I, where the definitions of each substituent are as described in the specification. The polymer has good film-forming properties. Curing occurs at 180°C, and the 5% weight loss temperature (T _d5% ) of the cured product is 440°C under a nitrogen atmosphere, and the carbon residue rate at 1000°C is as high as 49%. It can be used as a heat-resistant material in various fields such as aerospace and electronic appliances.

Description

Curable polyfluorenes and their applications as heat-resistant materials

technical field

The invention belongs to the technical field of high-performance polymer production, and specifically relates to a polymer containing trifluoroethyleneoxy and fluorene units that can be used as a heat-resistant material and a production method thereof.

Background technique

Fluorene polymers have attracted extensive attention due to their excellent heat resistance, thermo-oxidative stability, machinability, and good solubility in organic solvents, and have been deeply studied in many fields, especially as organic electroluminescent materials. (See Progress in Polymer Science. 2012, 37, 1192-1264). As a special class of high-performance materials, bisphenol fluorene polymers have been widely used in the electronic and electrical industries. For example, the epoxy resin with bisphenol fluorene as the structural unit is favored by the aerospace field and the electronic and electrical industry because of its high heat resistance and good processability. In addition, the bisphenol fluorene trifluoride developed by Dow Company Vinyl ether resins also have excellent heat resistance and dielectric properties (WO9015043). However, most of the bisphenol fluorene polymers are thermoplastic, and their thermal stability needs to be improved.

Fluorine-containing polyarylene ethers have excellent electrical properties, and have been widely used in aerospace, electronics, and other fields as high-performance films, molding compounds, and coatings (see Progress in Polymer Science 2010, 35, 1022–1077). At present, expensive perfluorobenzene is often used in the synthesis of fluorine-containing polyarylethers, resulting in a substantial increase in material costs. In recent years, perfluorocyclobutane (polyperfluorocyclobutane, PFCB) polymers derived from tetrafluoroethylene have been highly valued because of their relatively low cost, high temperature resistance, chemical Stability, excellent electrical properties, low moisture absorption and good mechanical properties, etc. (see WO9015043). With the development of non-fossil energy sources, fluorine-containing bisphenol fluorene polymers have been used as ion separators in fuel cells. However, most of these fluorine-containing polyaryl ethers are thermoplastic polymers, which are not good in terms of thermal stability.

To sum up, there is still a lack of a polymer material with low cost and good heat resistance in the art.

Contents of the invention

It is an object of the present invention to provide a polymer material which is relatively cost-effective and has good heat resistance.

The first aspect of the present invention provides a compound shown in the following formula I:

In the formula, R is selected from the following group: H, substituted or unsubstituted C1-C4 alkyl; wherein, the substitution is substituted by halogen;

In another preferred example, said R is selected from the group consisting of H, CH3.

The second aspect of the present invention provides a method for preparing the compound as described in the first aspect of the present invention, the method comprising the steps of:

In a polar solvent, under the action of zinc powder, the elimination reaction is carried out with the compound of formula Ia to obtain the compound of formula I;

In the above formulas, R is as defined above.

In another preferred example, the reaction is carried out in acetonitrile solvent.

In another preferred example, the elimination reaction takes 12-96 hours.

In another preferred example, the compound of formula Ia is prepared by the following method:

In a polar solvent, the compound of formula Ib is reacted with the compound of formula Ic to obtain the compound of formula Ia;

In the above formulas, R is as defined above.

In another preferred embodiment, the reaction is carried out in the presence of a base, preferably, the base is selected from the group consisting of cesium carbonate, potassium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate, or a combination thereof

In another preferred example, the polar solvent is selected from the group consisting of N-methylpyrrolidone, dimethyl sulfoxide, ethylene glycol dimethyl ether, tetrahydrofuran, or combinations thereof.

The third aspect of the present invention provides a polymer, the polymer has the structure shown in the following formula II:

In the formula, R is selected from the following group: H, substituted or unsubstituted C1-C4 alkyl; wherein, the substitution is substituted by halogen;

n≥2, preferably, n=2-1000, more preferably, n=10-200.

In another preferred embodiment, the polymer includes one or more features selected from the group consisting of:

The number average molecular weight of the polymer is 5000-50000; and/or

The polymer has a weight average molecular weight of 10,000 to 100,000; and/or

The degree of dispersion of the polymer is 1.3-6.0; and/or

Under a nitrogen atmosphere, the 5% thermal decomposition temperature (T _d5% ) of the polymer is ≥350°C, preferably ≥400°C, more preferably ≥420°C; and/or

Under air atmosphere, the 5% thermal decomposition temperature (T _d5% ) of the polymer is ≥350°C, preferably ≥380°C, more preferably ≥400°C; and/or

At 1000°C, the carbon residue rate of the polymer is ≥ 45%, preferably ≥ 48%; and/or

The initial curing temperature of the polymer is 145-165°C, preferably 150-160°C; and/or

The curing peak temperature of the polymer is 225-245°C, preferably 230-240°C.

A fourth aspect of the present invention provides a method for preparing a polymer as described in the third aspect of the present invention, said method comprising the following steps:

In an inert solvent, carry out oxidative polymerization with the compound of formula I as described in the first aspect of the present invention to obtain the polymer of formula II as described in the third aspect of the present invention;

In the formula, R is selected from the following group: H, substituted or unsubstituted C1-C4 alkyl; wherein, the substitution is substituted by halogen;

n≥2, preferably, n=2-1000, more preferably, n=10-200.

In another preferred example, the oxidative polymerization reaction temperature is -30-5°C, preferably -20°C-0°C.

In another preferred example, the oxidative polymerization reaction time is 5-48 hours.

In another preferred example, the method further includes: purifying the product of the oxidative polymerization reaction by column chromatography; preferably, the column chromatography includes: using neutral alumina (200 to 300 mesh) is the adsorbent, and the organic solvent is the eluent; more preferably, the organic solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone , or a combination thereof.

In another preferred example, the oxidative polymerization reaction is carried out in the presence of ferric salt; preferably, the ferric salt is selected from the group consisting of ferric chloride, ferric bromide, ferric sulfate, nitric acid Iron, or a combination thereof; more preferably, the ferric salt is ferric chloride.

In another preferred example, the molar ratio of the compound of formula I to the ferric salt is 1:1-10, preferably 1:2-5.

In another preferred example, the inert solvent is selected from the group consisting of nitrobenzene, dichloromethane, dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, or combinations thereof; preferably, The inert solvent is tetrachloroethane.

The fifth aspect of the present invention provides a cured product obtained by curing the polymer of formula II as described in the third aspect of the present invention.

In another preferred example, the cured product polymer has the structure shown in the following formula III:

Wherein, m is an integer, and m≤n.

In another preferred embodiment, the cured product is obtained by curing the polymer of formula II according to the fourth aspect of the present invention under heating conditions.

In another preferred example, the curing is carried out at 145-240°C.

The sixth aspect of the present invention provides a product, the product contains the polymer as described in the fourth aspect of the present invention or the cured product as described in the fifth aspect of the present invention, or the product is used as The polymer described in the fourth aspect of the present invention or the cured product as described in the fifth aspect of the present invention are prepared; preferably, when the product is prepared with the polymer described in the fourth aspect of the present invention , the article contains the cured product according to the fifth aspect of the present invention.

In another preferred example, the article is a polymer film.

In another preferred embodiment, the film is formed by a method selected from the group consisting of heating and pressing, solution spin coating, and solution drop coating.

In another preferred example, the solution used for the spin coating of the solution or the drip coating of the solution is an organic solvent solution of a polymer; preferably, the organic solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, Diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or combinations thereof.

It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described in the following (such as embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, we will not repeat them here.

Detailed ways

After long-term and in-depth research, the present inventor has prepared a polymer containing trifluoroethyleneoxy and fluorene units. The polymer has good heat resistance and processability, and is suitable as a durable polymer in the electrical and electronic industry. hot material. Based on the above findings, the inventors have accomplished the present invention.

the term

As used herein, the term "polymerized monomer containing trifluoroethyleneoxy and fluorene units" refers to a polymerized monomer containing trifluoroethyleneoxy and fluorene in its structure, preferably a compound of formula I.

The term "C1-C4 alkyl" refers to a straight or branched chain alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, or the like.

The term "substituted" means that one or more hydrogen atoms on the group are replaced by a substituent: halogen atom; wherein, the term "halogen" refers to fluorine, chlorine, bromine, iodine.

Polymerized monomers containing trifluoroethyleneoxy and fluorene units and their preparation

The invention provides a compound shown in the following formula I:

In the formula, R is selected from the following group: H, substituted or unsubstituted C1-C4 alkyl; wherein, the substitution is substituted by halogen. Preferably, said R is selected from the group consisting of H, -CH ₃ .

Said compound can be prepared by the following methods:

In an inert solvent, under the action of zinc powder, the compound of formula Ia is used for elimination reaction to obtain the compound of formula I. Preferably, the polar solvent is acetonitrile.

In another preferred example, the compound of formula Ia is prepared by the following method:

In an inert solvent, the compound of formula Ib is reacted with the compound of formula Ic to obtain the compound of formula Ia;

In the above formulas, R is as defined above.

In another preferred embodiment, the reaction is carried out in the presence of a base, preferably, the base is selected from the group consisting of potassium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate, or a combination thereof.

In another preferred example, the polar solvent is selected from the group consisting of N-methylpyrrolidone, dimethyl sulfoxide, ethylene glycol dimethyl ether, tetrahydrofuran, or combinations thereof

The preparation method of a kind of preferred formula I compound is as follows:

(1) 9,9'-bis(4-phenol)fluorene and tetrafluorodibromoethane in N-methylpyrrolidone or dimethyl sulfoxide (DMSO) in the presence of potassium hydroxide or potassium carbonate, React at room temperature for 10 to 20 hours to prepare 1-(2-bromo-1,1,2,2-tetrafluoroethoxy)naphthalene.

(2) In refluxing acetonitrile, 9,9-bis(4-2'-bromo-1'1'2'2'-tetrafluoroethoxyphenyl)fluorene undergoes an elimination reaction under the action of zinc powder, 9,9-Bis(4-1'2'2'-trifluoroethenyloxyphenyl)fluorene is obtained.

Polymers containing trifluoroethyleneoxy and fluorene units

The present invention also provides a polymer containing trifluoroethyleneoxy and fluorene units, the chemical structure of which is as follows:

Wherein, R is selected from the following group: H, substituted or unsubstituted C1-C4 alkyl; wherein, the substitution is substituted by halogen;

n≥2, preferably, n=2-1000, more preferably, n=10-200.

In a preferred example of the present invention, the number average molecular weight of the polymer is 10,000-100,000.

The polymer of the present invention has good heat resistance. In a preferred example of the present invention, under a nitrogen atmosphere, the 5% thermal decomposition temperature (T _d5% ) of the polymer is ≥ 350°C, preferably ≥400°C, more preferably ≥420°C. In another preferred embodiment of the present invention, under air atmosphere, the 5% thermal decomposition temperature (Td5%) of the polymer is ≥350°C, preferably ≥380°C, more preferably ≥400°C.

In a preferred example of the present invention, at 1000°C, the carbon residue rate of the polymer is ≥45%, preferably ≥48%, indicating that the polymer of the present invention has good heat resistance.

The polymer also has a wide curing temperature range, for example, in a preferred embodiment of the present invention, the initial curing temperature of the polymer is 145-165°C, preferably 150-160°C; The peak top temperature is 225-245°C, preferably 230-240°C. Due to the low initial curing temperature of the polymer, the required processing equipment is simple, indicating that the polymer has good processability.

The polymer containing trifluoroethyleneoxy and fluorene units in the present invention can be heated and molded to obtain a polymer sheet, or prepared into a solution to form a film by spin coating or drop coating to obtain a polymer film. The solution used for spin coating or drop coating is obtained by dissolving the polymer in an organic solvent. Described organic solvent is toluene, xylene, mesitylene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl One or a mixture of sulfoxide or N-methylpyrrolidone.

Preparation of polymers containing trifluoroethyleneoxy and fluorene units

The present invention also provides a kind of preparation method of described polymer, described method comprises the following steps:

In an inert solvent, carry out oxidative polymerization with a compound of formula I to obtain a polymer of formula II;

In the formula, R is selected from the following group: H, substituted or unsubstituted C1-C4 alkyl; wherein, the substitution is substituted by halogen;

n≥2, preferably, n=2-1000, more preferably, n=10-200.

In another preferred example, the oxidative polymerization reaction temperature is -30-5°C, preferably -15°C-0°C.

In another preferred example, the oxidative polymerization reaction time is 5-48 hours.

The reaction product can optionally be purified by conventional methods in the art. In another preferred embodiment, the product of the oxidative polymerization reaction is purified by column chromatography; preferably, the column chromatography The analysis includes: using neutral alumina (200 to 300 mesh) as an adsorbent, and using an organic solvent as an eluent; preferably, the organic solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, diphenyl Ether, cyclohexanone, chloroform, acetone, or combinations thereof.

The oxidative polymerization reaction can be carried out under conventional oxidative polymerization reaction conditions, for example, it can be carried out in the presence of a ferric salt; preferably, the ferric salt is selected from the group consisting of ferric chloride, bromide Iron, ferric sulfate, ferric nitrate, or a combination thereof; more preferably, the ferric salt is ferric chloride.

In another preferred example, the molar ratio of the compound of formula I to the ferric salt is 1:1-10, preferably 1:2-5.

The inert solvent is not particularly limited, including (but not limited to) a solvent selected from the group consisting of nitrobenzene, dichloromethane, dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, or Its combination; Preferably, the inert solvent is tetrachloroethane.

The main advantages of the present invention include:

(1) A polymer monomer with a novel structure is provided, and the polymer monomer can be used to prepare a polymer with good heat resistance.

(2) A polymer containing trifluoroethyleneoxy and fluorene units is provided, and the preparation method of the polymer is simple and has good film-forming properties.

(3) A polymer film product containing trifluoroethyleneoxy and fluorene units is provided. In a preferred example, the obtained film has a 5% weight loss temperature (T _d5% ) of 440 °C under a nitrogen atmosphere. ℃, and the carbon residue rate at 1000 ℃ is as high as 49%, which is very suitable for heat-resistant materials in the electrical and electronic industry. The cured product can be used as enameled wire coating.

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. For the experimental methods without specific conditions indicated in the following examples, the conventional conditions or the conditions suggested by the manufacturer are usually followed. Percentages and parts are by weight unless otherwise indicated.

Example 1 Precursor 1——Preparation of 9,9-two (4-2'-bromo-1'1'2'2'-tetrafluoroethoxyphenyl) fluorene

Under argon protection, 7.008 grams of 9,9-bis(4-hydroxyphenyl)fluorene, 19.875 grams of cesium carbonate and 50 milliliters of DMSO (dimethyl sulfoxide) were added to a 100 milliliter three-necked flask, and 6 Milliliter 1,2-dibromotetrafluoroethane and stirred at room temperature for 3 hours, rose to 70 ° C for 16 hours, stopped heating, cooled to room temperature, poured the reaction mixture solution into 500 ml of water, stirred vigorously for 10 minutes, batch Once extracted with ethyl acetate, the organic phase was washed three times with saturated aqueous sodium chloride solution and dried with anhydrous sodium sulfate, filtered, the filter cake was washed with ethyl acetate, the solvent was removed by rotary evaporation, and 6.665 grams of white solid was obtained by n-hexane column chromatography. Yield 47%. Proton spectrum characterization ( ¹ HNMR, 400MHz, (CD ₃ ) ₂ CO, δinppm): 7.91～7.95(d,2H), 7.48～7.52(d,2H), 7.40～7.47(dt,2H), 7.29～7.38( m, 6H), 7.21～7.27(d, 4H); fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, (CD ₃ ) ₂ CO, δinppm): -70.06, (t, 4F), -86.58(t, 4F).

Example 2 Precursor 1——Preparation of 9,9-two (4-2'-bromo-1'1'2'2'-tetrafluoroethoxyphenyl) fluorene

Under the protection of argon, add 34.964 g of 9,9-bis(4-hydroxyphenyl)fluorene, 114.037 g of cesium carbonate and 170 ml of DMSO (dimethyl sulfoxide) into a 500 ml three-necked flask, and bubble the argon for 1 hour , slowly add 35 ml of 1,2-dibromotetrafluoroethane dropwise under stirring and stir at room temperature for 2 hours, rise to 70 ° C and react for 13 hours, then stop heating, cool to room temperature, filter to remove inorganic salts, and pour the filtrate into 1 liters of water, stirred vigorously for 10 minutes, extracted with ethyl acetate in batches, washed the organic phase three times with saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate, filtered, washed the filter cake with ethyl acetate, spin-dried, and weighed petroleum ether. Crystallized to obtain 50 g of light yellow solid, yield 71%. Proton spectrum characterization ( ¹ HNMR, 400MHz, (CD ₃ ) ₂ CO, δinppm): 7.91～7.95(d,2H), 7.48～7.52(d,2H), 7.40～7.47(dt,2H), 7.29～7.38( m, 6H), 7.21～7.27(d, 4H); fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, (CD ₃ ) ₂ CO, δinppm): -70.06, (t, 4F), -86.58(t, 4F).

Example 3 Precursor 2——Preparation of 9,9-bis(4-1'2'2'-trifluoroethyleneoxyphenyl)fluorene

Under argon protection, add 6.000 grams of 9,9-bis(4-2'-bromo-1'1'2'2'-tetrafluoroethoxyphenyl) fluorene and 2.642 grams of activated zinc powder into a 250 ml three-necked flask and 60 ml of freshly distilled acetonitrile, heated to reflux and stirred for 36 hours, then stopped heating, cooled to room temperature, filtered to remove inorganic matter, rotary evaporated to remove most of the acetonitrile, poured into 100 ml of water, extracted with ethyl acetate, and the extract was saturated with chlorinated The sodium solution was washed three times, the organic phase was dried with anhydrous sodium sulfate, filtered, the filter cake was washed with ethyl acetate, the solvent was removed by rotary evaporation, and 2.781 g of a white solid was obtained by n-hexane column chromatography, with a yield of 64%. Proton spectrum characterization ( ¹ HNMR, 400MHz, (CD ₃ ) ₂ CO, δinppm): 7.88～7.94(d,2H), 7.44～7.49(d,2H), 7.38～7.44(dt,2H), 7.30～7.36( dt, 2H), 7.23～7.29(m, 4H), 7.10～7.17(d, 4H); fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, (CD ₃ ) ₂ CO, δinppm): -135.25～-135.81(dd, 2F), -128.06～-128.68(dd, 2F), -120.90～-121.38(dd, 2F).

Example 4 Precursor 2——Preparation of 9,9-bis(4-1'2'2'-trifluoroethyleneoxyphenyl)fluorene

Under argon protection, add 48.970 grams of 9,9-bis(4-2'-bromo-1'1'2'2'-tetrafluoroethoxyphenyl) fluorene and 14.642 grams of activated zinc powder into a 500 ml three-necked flask and 160 ml of freshly distilled acetonitrile, heated to reflux and stirred for 48 hours, then stopped heating, cooled to room temperature, filtered to remove inorganic matter, rotary evaporated to remove most of the acetonitrile, poured into 200 ml of water, extracted with ethyl acetate, and the extract was saturated with chlorinated The sodium solution was washed three times, the organic phase was dried with anhydrous sodium sulfate, filtered, the filter cake was washed with ethyl acetate, the solvent was removed by rotary evaporation, and 17.180 g of white solid was obtained by n-hexane column chromatography and recrystallized, with a yield of 49%. Proton spectrum characterization ( ¹ HNMR, 400MHz, (CD ₃ ) ₂ CO, δinppm): 7.88～7.94(d,2H), 7.44～7.49(d,2H), 7.38～7.44(dt,2H), 7.30～7.36( dt, 2H), 7.23～7.29(m, 4H), 7.10～7.17(d, 4H); fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, (CD ₃ ) ₂ CO, δinppm): -135.25～-135.81(dd, 2F), -128.06～-128.68(dd, 2F), -120.90～-121.38(dd, 2F).

The preparation of embodiment 5 polymer

Under argon protection, add 1.02 g of 9,9-bis(4-1'2'2'-trifluoroethyleneoxyphenyl)fluorene and 5 ml of 1,1,2,2-tetrachloro Ethane, stir to dissolve it, add 0.811 gram of anhydrous ferric chloride and 7 milliliters of 1,1,2,2-tetrachloroethane in another 50 milliliter Schlenk reaction flask, bubble for 30 minutes at the same time, and then 5 mL of 1,1,2,2-tetrachloroethane solution containing 9,9-bis(4-1'2'2'-trifluoroethyleneoxyphenyl)fluorene was transferred to anhydrous ferric chloride , stirred at -5°C for 24 hours. After the reaction, the reaction solution was poured into methanol containing a small amount of concentrated hydrochloric acid, and the obtained yellow precipitate was filtered and dried to obtain a crude polymer. GPC test (tetrahydrofuran as eluent, polystyrene standard) showed that the number average molecular weight of the polymer was 13000, the weight average molecular weight was 62400, and the dispersion degree was 4.8. Proton spectrum characterization ( ¹ HNMR, 400MHz, DMSO-d6, δinppm): 5.97～8.39(m). Fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, DMSO-d6, δinppm): -133.70～-135.41(m, 2F), -125.98～-127.58(m, 2F), -118.27～-119.82(m, 2F).

The preparation of embodiment 6 polymer

Same as Example 5, but the polymerization reaction temperature is -10°C. The obtained polymer was tested by GPC (tetrahydrofuran as eluent, polystyrene standard), which showed that its number average molecular weight was 11500, its weight average molecular weight was 32800, and its dispersity was 2.85. Proton spectrum characterization ( ¹ HNMR, 400MHz, DMSO-d6, δinppm): 5.98～8.39(m). Fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, DMSO-d6, δinppm): -133.70～-135.41(m, 2F), -125.98～-127.58(m, 2F), -118.27～-119.82(m, 2F).

The preparation of embodiment 7 polymer

Same as Example 5, but the polymerization reaction temperature is -15°C. The obtained polymer was tested by GPC (tetrahydrofuran as eluent, polystyrene standard), which showed that its number average molecular weight was 6400, its weight average molecular weight was 12000, and its dispersity was 1.87. Proton spectrum characterization ( ¹ HNMR, 400MHz, DMSO-d6, δinppm): 5.98～8.39(m). Fluorine spectrum characterization ( ¹⁹ FNMR, 376MHz, DMSO-d6, δinppm): -133.70～-135.41(m, 2F), -125.98～-127.58(m, 2F), -118.27～-119.82(m, 2F).

The purification of embodiment 8 polymkeric substance

Purification of the polymer is necessary to remove iron ions that may be contained in the polymer. The specific purification steps are as follows:

Get 200 milligrams of polymers obtained in the above-mentioned Examples 5 to 7, dissolve them in 3 milliliters of toluene respectively, inject the obtained solution into a glass column with a length of 10 centimeters and a diameter of 2 centimeters filled with 200 mesh neutral alumina, and use about Rinse with 200 ml of toluene, collect the eluent, concentrate to a volume of about 2 ml, settle in a large amount of methanol, let stand and decant the supernatant, collect the solid by suction filtration, and vacuum dry at 70°C for 12 hours. A white solid was obtained. ICP-MASS test shows that the iron content in the polymer is less than 1ppm.

Curing Behavior of Example 9 Polymer

The purified polymers obtained in Example 8 above were placed in a differential scanning calorimeter, heated from 50°C to 300°C at a heating rate of 10°C/min, and the thermal curing temperature of the polymer was measured. The obtained results are shown in Table 1. Wherein, polymers P1-P3 respectively represent the polymer samples obtained in Examples 5-7 and purified in Example 8.

After the polymer is cured, the chemical structure of its cured product is shown below.

Table 1 The curing temperature of the polymer

polymer Initial curing temperature (°C) Curing peak temperature (°C) P1 155 238 P2 159 238 P3 150 232

It can be seen from Table 1 that the polymer has a wide curing temperature range, and the initial curing temperature is low, indicating that the polymer has excellent processability.

The heat resistance of embodiment 10 polymer

The purified polymer obtained in Example 8 above was spin-coated into a thin film, then the polymer thin film was put into a quartz tube furnace and crushed, and placed in a thermogravimetric analyzer at a temperature of 10°C/min. Heating rate, testing the thermal decomposition temperature and carbon residue of the polymer. The obtained results are shown in Table 2.

Table 2 Polymer thermogravimetric loss temperature and residual rate in nitrogen under nitrogen and air atmosphere

All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims (15)

1. a polymkeric substance, is characterized in that, described polymkeric substance has as shown in the formula the structure shown in II:

In formula, R is selected from lower group: H, substituted or unsubstituted C1-C4 alkyl; Wherein, described replacement is optionally substituted by halogen;

n≥2。

2. polymkeric substance as claimed in claim 1, is characterized in that, n=2-1000.

3. polymkeric substance as claimed in claim 1, is characterized in that, n=10 ~ 200.

4. polymkeric substance as claimed in claim 1, it is characterized in that, described polymkeric substance comprises the one or more features being selected from lower group:

The number-average molecular weight of described polymkeric substance is 5000 ~ 50000; And/or

The weight-average molecular weight of described polymkeric substance is 10000 ~ 100000; And/or

The dispersity of described polymkeric substance is 1.3 ~ 6.0; And/or

In a nitrogen atmosphere, 5% heat decomposition temperature (T of described polymkeric substance _d5%) be>=350 DEG C; And/or

In air atmosphere, 5% heat decomposition temperature (T of described polymkeric substance _d5%) be>=350 DEG C; And/or

At 1000 DEG C, the carbon yield of described polymkeric substance is >=45%; And/or

The initial cure temperature of described polymkeric substance is 145-165 DEG C; And/or

The solidification summit temperature of described polymkeric substance is 225-245 DEG C.

5. polymkeric substance as claimed in claim 1, it is characterized in that, described polymkeric substance comprises the one or more features being selected from lower group:

In a nitrogen atmosphere, 5% heat decomposition temperature (T of described polymkeric substance _d5%) be>=400 DEG C; And/or

In air atmosphere, 5% heat decomposition temperature (T of described polymkeric substance _d5%) be>=380 DEG C; And/or

At 1000 DEG C, the carbon yield of described polymkeric substance is >=48%; And/or

The initial cure temperature of described polymkeric substance is 150-160 DEG C; And/or

The solidification summit temperature of described polymkeric substance is 230-240 DEG C.

6. polymkeric substance as claimed in claim 1, it is characterized in that, described polymkeric substance comprises the one or more features being selected from lower group:

In a nitrogen atmosphere, 5% heat decomposition temperature (T of described polymkeric substance _d5%) be>=420 DEG C; And/or

In air atmosphere, 5% heat decomposition temperature (T of described polymkeric substance _d5%) be>=400 DEG C.

7. the preparation method of polymkeric substance as claimed in claim 1, is characterized in that, comprise the following steps:

In inert solvent, carry out oxidative polymerization with such as formula I, obtain formula II polymkeric substance as claimed in claim 1;

In formula, R is selected from lower group: H, substituted or unsubstituted C1-C4 alkyl; Wherein, described replacement is optionally substituted by halogen;

n≥2。

8. method as claimed in claim 7, is characterized in that, described oxidative polymerization carries out under trivalent iron salt exists.

9. method as claimed in claim 7, it is characterized in that, described trivalent iron salt is selected from lower group: iron(ic) chloride, iron bromide, ferric sulfate, iron nitrate, or its combination.

10. method as claimed in claim 7, it is characterized in that, described trivalent iron salt is iron(ic) chloride.

11. methods as claimed in claim 7, it is characterized in that, described inert solvent is selected from lower group: oil of mirbane, methylene dichloride, ethylene dichloride, tetrachloroethane, chlorobenzene, dichlorobenzene, or its combination.

12. 1 kinds of cured products, is characterized in that, described cured product is cured with formula II polymkeric substance as claimed in claim 4 and obtains.

13. cured products as claimed in claim 12, it is characterized in that, described cured product polymkeric substance has the structure shown in following formula III:

Wherein, m is integer, and m≤n.

14. 1 kinds of goods, it is characterized in that, described goods are containing, for example polymkeric substance according to claim 1 or cured product as claimed in claim 12, or prepared by described goods polymkeric substance as claimed in claim 1 or cured product as claimed in claim 12.

15. goods as claimed in claim 14, it is characterized in that, prepared by described goods polymkeric substance as claimed in claim 1, and described goods are containing, for example cured product according to claim 12.